JP5578406B2 - One-part moisture curable sealant composition for improving antibacterial and antifungal properties of outer wall joint top coating film, and method for improving antibacterial and antifungal properties of outer wall joint top coating film using the same - Google Patents

Description

The present invention is a rubber-like elastic body that is cured by moisture in the air, etc., has excellent storage stability and stain resistance of the top coat film, and improves the antibacterial and antifungal properties of the outer wall joint top coat film. The present invention relates to a liquid-type moisture-curable sealant composition and a method for improving the antibacterial and antifungal properties of an outer wall joint top coat using the same.

Many sealing materials are used for the purpose of waterproofing, design, and the like on the outer wall joints of building structures and civil engineering structures. These sealing materials prevent the intrusion of rainwater into the structure from the joints between the mortar board, concrete board, ALC board, and the outer wall of metal materials, etc., as well as temperature differences and wind pressure due to earthquakes and solar radiation. Therefore, it is required to alleviate the distortion of the outer wall material caused by the above, to prevent the destruction of the outer wall material, and to not impair the appearance of the outer wall. For this reason, the sealing material is excellent in workability and adhesiveness to various outer wall materials, and absorbs various joint displacements caused by expansion and contraction of members caused by temperature differences depending on the climate, wind pressure, earthquakes, etc. Therefore, the rubber properties after curing are designed to be soft with low modulus and large elongation.
Moreover, the outer wall part of a building structure or a civil engineering structure is often overcoated with a paint having excellent durability on the outer wall material. This top coat has the original function of preventing rainwater from entering by the coating film formed, protecting the outer wall material from heat deterioration and ultraviolet light deterioration due to solar radiation, and maintaining the aesthetics of the outer wall. It plays an important role in the design that determines the quality of objects and civil engineering structures. In order to improve the aesthetics and make it look more natural, the paint used in this top coat must be blended with various types of inorganic and organic particles, balloons, etc. in the paint, and use various paint patterns. The shape and properties of the surface are complicated.

  However, in recent years, if the sealing material contains a lot of incompatible liquids, after the sealing material is cured, the liquid component moves from the sealing material to the overcoated film (bleeds), and the top coated film becomes sticky. As a result, dirt such as dust and soot floating in the air adheres to the surface of the paint film, resulting in contamination of the paint film on the outer wall surface (vertical and horizontal strip lines). ), A problem that impairs the aesthetics (in terms of design) that contamination occurs, and countermeasures are being studied. Furthermore, the so-called water supply that occurs when rainwater flows down the outer wall surface and the top coat film of the outer wall joints generate algae, mold, etc., causing problems that impair the aesthetics (design), and countermeasures are also being considered. (Patent Documents 1, 2, and 3).

  First, the present applicants disclosed in Patent Document 1; “Sealing material composition suitable for top coating specification, and method for applying sealing material using the same”, an isocyanate group-containing urethane prepolymer and a specific amount of low molecular weight. A sealing material composition containing a plasticizer and a high molecular weight plasticizer has been found and proposed that it has excellent rubber elastic properties, the coated film does not easily crack or crack, and does not bleed. In the exposure, it is observed that mold is generated on the coating on the outer wall joint part, and prevention of mold generation is required.

JP-A-6-41516 JP-A-10-176163 JP 2003-86443 A JP 2006-143760 A

  The present invention is excellent in storage stability and joint contamination resistance in the exterior wall coating specification of a building structure or the like to be overcoated, and can suppress the generation of bacteria and mold on the exterior wall joint top coating film over a long period of time. It is an object of the present invention to provide a one-component moisture-curing sealant composition and a method for improving the storage stability and antibacterial and antifungal properties of the outer wall joint top coat using the same.

As a result of intensive studies on the above problems, the inventor of the present invention has a one-component moisture containing an isocyanate group-containing urethane prepolymer (A), an antibacterial / antifungal agent (B), and a high molecular weight dilution resin (C). By filling and using the curable sealant composition on the outer wall joints of the top coating specification, and using the antibacterial / antifungal agent (B) as a specific antibacterial / antifungal agent, The one-component moisture-curable sealant composition is excellent in workability and storage stability, the cured product has good rubber elastic properties, and the one-component moisture-curable sealant composition is used as an outer wall joint. It was found that the use of the coating prevents contamination of the top coating film, suppresses the generation of bacteria and mold on the outer wall joint top coating film, and makes it excellent in design.
The reason for improving the stain resistance, antibacterial and antifungal properties of the outer wall joint top coat by the above configuration is not clear, but it is contained in the one-component moisture-curable sealing material composition (liquid at room temperature). average molecular weight of 500 or less ingredients that have a specified amount, and) the use of high molecular weight diluent resin (C) is believed to prevent the occurrence of bleeding contamination, or, antibacterial and antifungal layered silicate By using a specific method of adding a specific antibacterial / antifungal agent (B), which is a composite carrying a functional compound, as a dispersion dispersed in a high molecular weight dilution resin (C), it can be used for a long time. It is thought that all antibacterial and antifungal properties are imparted. The one-pack type moisture curable sealant composition for improving the antibacterial and antifungal properties of the outer wall joint top coat of the present invention preferably does not contain low molecular weight plasticizers such as acid esters and dioctyl phthalate. However, liquid components at room temperature with an average molecular weight of 500 or less, such as solvents and tung oil, diffuse little by little, and the liquid urethane-based resin diffuses little by little at room temperature. It is thought that antibacterial properties and fungicidal properties are imparted over a wide range.

That is, the present invention is the following (1) to (1 1 ).
(1) An outer wall joint top coating film comprising an isocyanate group-containing urethane prepolymer (A) and a dispersion in which an antibacterial / antifungal agent (B) is dispersed in a high molecular weight dilution resin (C) . A one-component moisture-curing sealant composition that improves antibacterial and antifungal properties ,
The antibacterial and antifungal properties of the above outer wall joint top coating film, wherein the antibacterial and antifungal agent (B) is a composite in which a layered silicate is loaded with an antibacterial and antifungal compound . -Pack type moisture curable sealant composition for improving the quality.
(2) The antibacterial of the outer wall joint top coating film of (1) above, wherein the content of the liquid component at room temperature with an average molecular weight of 500 or less in the one-component moisture-curable sealant composition is 12% by mass or less -Pack type moisture-curing sealant composition that improves water and mold resistance.
(3) The antibacterial and antibacterial properties of the outer wall joint top coating film of (1) or (2), wherein the high molecular weight dilution resin (C) is a liquid resin at room temperature having a number average molecular weight of 1,000 or more. A one-component moisture-curable sealant composition that improves moldability.
(4) The one-pack type moisture curable sealant composition that improves the antibacterial and antifungal properties of the outer wall joint part top coat of (3), wherein the resin is a urethane resin.
(5) One-component moisture that improves the antibacterial and antifungal properties of the outer wall joint top coating film of (4), wherein the urethane resin is a reaction product of a polyoxyalkylene alcohol and an organic isocyanate. A curable sealant composition.
(6) One-component moisture that further improves the antibacterial and antifungal properties of the outer wall joint top coating film of any one of (1) to (5), which further comprises an oxygen curable unsaturated compound (D) A curable sealant composition.
(7) The antibacterial properties of the outer wall joint top coating film of (6), wherein the oxygen curable unsaturated compound (D) is one or more selected from the group consisting of a drying oil and a modified product thereof. A one-component moisture-curing sealant composition that improves mold resistance.
(8) A one-component moisture-curable sealant composition that further improves the antibacterial and antifungal properties of the outer wall joint top coating film according to any one of (1) to (7), further containing an additive.
(9) The additive is selected from the group consisting of fillers, high molecular weight plasticizers, weathering stabilizers, wrinkle modifiers, adhesion promoters, curing accelerators, storage stability improvers, colorants and solvents. A one-component moisture-curable sealant composition that improves the antibacterial and antifungal properties of the outer wall joint joint top coat of (8), which is one type or two or more types.
(10) A one-component moisture-curing sealing material composition for improving the antibacterial and antifungal properties of the outer wall joint part top coat film of any one of the above (1) to (9) is applied to the outer wall joint part of the building structure. A method for improving the antibacterial and antifungal properties of the outer wall joint top coating film, which comprises filling, and then applying a coating to the surface of the building structure including the outer wall joint and curing.
(11) Before filling the outer wall joint part of the building structure with the one-part moisture curable sealant composition that improves the antibacterial and antifungal properties of the outer wall joint part top coat, A method for improving the antibacterial and antifungal properties of the outer wall joint joint top coat of (10), wherein a primer is applied.

  For the first time according to the present invention, it is excellent in storage stability and joint contamination resistance in the exterior wall coating specification of a building structure or the like to be overcoated, and suppresses the generation of bacteria and mold on the exterior wall joint top coating film over a long period of time. It has become possible to provide a one-component moisture-curing sealant composition that can be produced, and a method for improving the storage stability and antibacterial and antifungal properties of the outer wall joint top coat using the same.

The present invention will be described in detail below.
Isocyanate group-containing urethane prepolymer (A) in the present invention, the isocyanate groups react with moisture in the air (humidity), cross-linked to form a urea linkage, intended to cure, the outer wall joints top coating film of the present invention The one-component moisture-curing sealant composition that improves the antibacterial and antifungal properties of the composition is used as a curing component, and an organic polyisocyanate and an active hydrogen-containing compound are added to the active hydrogen (group) with an isocyanate group. It is obtained by reacting in excess conditions.

Specific examples of the organic polyisocyanate include diphenylmethane diisocyanate (MDI) such as phenylene diisocyanate, diphenyl diisocyanate, naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, and 2,4-toluene. Diisocyanates, toluene diisocyanates (TDI) such as 2,6-toluene diisocyanate, aromatic diisocyanates such as diphenyl ether diisocyanate, araliphatic diisocyanates such as xylylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, propylene diisocyanate, butylene diisocyanate Aliphatic diisocyanate, cyclohexane diisocyanate , Alicyclic diisocyanates such as methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate, and carbodiimide-modified, biuret-modified, allophanate-modified, dimer, trimer, and polymethylene polyphenyl polyisocyanate of these diisocyanates (Crude MDI, polymeric MDI) etc. are mentioned, These can be used individually or in combination of 2 or more types.
Of these, aromatic diisocyanates and araliphatic diisocyanates are preferable, MDIs are more preferable, and 4,4′-diphenylmethane diisocyanate is particularly preferable in terms of excellent tensile adhesiveness and water resistance after curing.
In addition, organic monoisocyanates such as n-butyl monoisocyanate, n-hexyl monoisocyanate, n-tetradecyl monoisocyanate, n-octadecyl monoisocyanate, p-isopropylphenyl monoisocyanate are also used for modification of the isocyanate group-containing urethane prepolymer. Can be used.

  Examples of the active hydrogen-containing compound include a polymer polyol and a polymer polyamine, a chain extender used in some cases, and a polymer or low-molecular monool used for modifying an isocyanate group-containing urethane prepolymer.

  Examples of the polymer polyol include, for example, polyester polyol, polycarbonate polyol, polyoxyalkylene polyol, hydrocarbon polyol, polyacrylate polyol, polymethacrylate polyol, animal and plant polyol, these copolyols, or two or more of these. And the like. The number average molecular weight of the polymer polyol is 500 or more, more preferably 1,000 to 100,000, still more preferably 1,000 to 30,000, and particularly preferably 1,000 to 20,000. When the number average molecular weight is less than 500, rubber elastic properties such as elongation after curing of the obtained one-component moisture-curable sealing material composition deteriorate, and when it exceeds 100,000, the resulting isocyanate group-containing urethane prepolymer This is not preferable because the viscosity becomes too high and the workability deteriorates.

  Examples of the polyester polyol include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalenedicarboxylic acid, triphthalic acid, and the like. One or more of polycarboxylic acids such as merit acid, acid esters, or acid anhydrides, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9- Nonanediol, diethylene glycol, dipropylene glycol, 1 , 4-cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, low molecular polyols such as trimethylolpropane, glycerin, pentaerythritol, butylenediamine, hexamethylenediamine, xylylenediamine, isophoronediamine, etc. Examples thereof include polyester polyols or polyester amide polyols obtained by a dehydration condensation reaction with one or more low molecular amino alcohols such as low molecular polyamines, monoethanolamine, and diethanolamine. Also, for example, lactone polyesters obtained by ring-opening polymerization of cyclic ester (lactone) monomers such as ε-caprolactone and γ-valerolactone using low molecular polyols, low molecular polyamines, and low molecular amino alcohols as initiators. A polyol is mentioned.

  Examples of the polycarbonate polyol include dehydrochlorination reaction of low molecular polyols and phosgene used for the synthesis of the above-described polyester polyol, or esters of the low molecular polyols with diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and the like. What is obtained by an exchange reaction is mentioned.

Examples of the polyoxyalkylene polyol include low molecular polyols, low molecular polyamines, low molecular amino alcohols, polycarboxylic acids, sorbitol, mannitol, sucrose used for the synthesis of the above-described polyester polyols. 1 or more of cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using one or more of low molecular weight polyhydric alcohols such as saccharides such as glucose and low molecular weight polyphenols such as bisphenol A and bisphenol F as initiators A polyoxyethylene-based polyol, a polyoxypropylene-based polyol, a polyoxybutylene-based polyol obtained by ring-opening addition polymerization or copolymerization (hereinafter, “polymerization or copolymerization” is referred to as “(co) polymerization”), Polio Tetramethylene-based polyols, poly- (oxyethylene)-(oxypropylene) -random or block (co) polymerized polyols, polyester ether polyols, polycarbonate ether polyols, and the like, which are the aforementioned polyester polyols and polycarbonate polyols as initiators. Can be mentioned. Moreover, the polyol which made these various polyols and organic isocyanate react by hydroxyl group excess with respect to an isocyanate group, and made the molecular terminal a hydroxyl group is also mentioned. The number of average alcoholic hydroxyl groups per molecule of the polyoxyalkylene polyol is preferably 2 or more, more preferably 2 to 4, and particularly preferably 2 to 3.
Furthermore, the polyoxyalkylene-based polyol is produced at the time of production thereof by cesium hydride, cesium methoxide, cesium alkoxide such as cesium ethoxide, cesium-based compounds such as cesium hydroxide, diethyl zinc, iron chloride, metalloporphyrin, phosphazenium compound, The total unsaturation obtained by using a double metal cyanide complex such as a double metal cyanide complex such as a zinc hexacyanocobaltate glyme complex or diglyme complex as a catalyst is 0.1 meq / g or less. 07 meq / g or less, particularly 0.04 meq / g or less is preferable, and molecular weight distribution [ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene by gel permeation chromatography (GPC) = Mw / Mn] is 1.6 or less, especially 1.0 A narrow one of 1.3 is able to lower the viscosity of the resulting isocyanate group-containing urethane prepolymer, and the rubber elastic properties after curing of the resulting one-component moisture-curable sealing material composition are improved. preferable.
In addition, for modification of an isocyanate group-containing urethane prepolymer, polyoxyl obtained by ring-opening addition polymerization of a cyclic ether compound such as propylene oxide using a low-molecular monoalcohol such as methyl alcohol, ethyl alcohol or propyl alcohol as an initiator. In some cases, polyoxyalkylene monools such as propylene monools may be used.
The “system” such as the polyoxyalkylene-based polyol or polyoxyalkylene-based monool is 50% by mass or more, further 80% by mass or more, particularly preferably 90% by mass of the portion excluding the hydroxyl group in 1 mol of the molecule. % Or more is composed of polyoxyalkylene, which means that the remaining part may be modified with ester, urethane, polycarbonate, polyamide, poly (meth) acrylate, polyolefin, etc., except for hydroxyl groups. Most preferably, 95% by mass or more of the molecules consist of polyoxyalkylene.

  Examples of the hydrocarbon-based polyol include, for example, polyolefin polyols such as polybutadiene polyol and polyisoprene polyol, polyalkylene polyols such as hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol, and halogenated poly such as chlorinated polypropylene polyol and chlorinated polyethylene polyol. Examples include alkylene polyols.

As the poly (meth) acrylate-based polyol (hereinafter, “(meth) acrylate” means “acrylate or methacrylate”), (meth) acrylate monomers containing a hydroxyl group such as hydroxyethyl (meth) acrylate And other (meth) acrylic acid alkyl ester monomers (hereinafter, “(meth) acrylic” means “acrylic or methacrylic”) in the presence or absence of a radical polymerization initiator. And the like.
Examples of animal and plant-based polyols include castor oil-based diols.

  Examples of the polymer polyamine include polyoxyalkylene polyamines having a number average molecular weight of 500 or more and a polyoxyalkylene polyol having an amino group at the terminal, such as a terminal diaminated product of polypropylene glycol.

  As the chain extender, in addition to the low molecular weight polyols, polyamines, amino alcohols used in the synthesis of the polyester polyol, the above-mentioned polyoxyalkylene polyols having a low molecular weight with a number average molecular weight of less than 500 can be used. Illustrated.

  Any of the compounds listed as active hydrogen-containing compounds can be used alone or in combination of two or more. Among these compounds, the rubber elastic properties of the resulting one-component moisture-curable sealant composition In view of good adhesion and high molecular weight, polymer polyols are preferred, polyoxyalkylene polyols are more preferred, and polyoxypropylene polyols are most preferred.

  The isocyanate group-containing urethane prepolymer (A) can be synthesized by either a batch charge reaction method or a multistage charge reaction method, but it is necessary to leave an isocyanate group in the molecule of the prepolymer. The equivalent ratio of isocyanate group / active hydrogen (group) of the isocyanate group of the organic polyisocyanate to the active polyol (group) of the active hydrogen-containing compound such as a chain extender and a polymer polyol or polymer polyamine is 1. 1 to 5.0 / 1.0 is preferable, and 1.3 to 2.0 / 1.0 is more preferable. The isocyanate group-containing urethane prepolymer (A) thus obtained preferably has an isocyanate group content of 0.1 to 15.0% by mass, particularly preferably 0.3 to 10.0% by mass, and most preferably 0. 0.4 to 5.0% by mass. When the isocyanate group content is less than 0.1% by mass, the molecular weight becomes too large, the viscosity increases, and the workability decreases. Moreover, since there are few crosslinking points in a prepolymer, sufficient adhesiveness cannot be obtained. When the isocyanate group content exceeds 15.0% by mass, it is difficult to prevent foaming due to carbon dioxide gas generated by the reaction of the isocyanate group with moisture, such being undesirable.

  For the synthesis of the isocyanate group-containing urethane prepolymer (A), a known catalyst similar to the compounds mentioned as the curing acceleration catalyst described later can be used as the urethanization catalyst. Among these, metal organic acid salts and salts of organic metals and organic acids are preferable, and dibutyltin dilaurate is particularly preferable. Furthermore, a known organic solvent can be used.

  The antibacterial / antifungal agent (B) in the present invention is a composite in which a layered silicate is loaded with an antibacterial / antifungal compound, and the antibacterial / antifungal compound exhibits antibacterial and antifungal properties. Any inorganic compound and organic compound can be used without any particular limitation.

Examples of the inorganic compound having antibacterial and antifungal properties include, for example, silver, copper, zinc antibacterial and antifungal metal ion salts or oxides, which are various carriers, such as activated carbon, activated alumina, Examples thereof include those supported on apatite, zeolite, silica gel, zirconium phosphate, titanium phosphate and the like.
There are no particular restrictions on the method of supporting these metal ions on the inorganic compound, and any of the known supporting methods can be adopted, for example, a method of supporting by physical adsorption or chemical adsorption, or by ion exchange reaction. Examples thereof include a method, a method of supporting with a binder, a method of forming a thin layer on the surface of an inorganic compound by a thin film forming method such as vapor deposition, dissolution and precipitation, and sputtering.

Examples of the organic compounds having antibacterial and antifungal properties include thiazole compounds and imidazole compounds.
Specific examples of the thiazole compound include 4,5-benzoisothiazol-3-one, 4- (n-octyl) isothiazolin-3-one, 4-methyl-5-chloroisothiazolin-3-one, 4 -Methylisothiazolin-3-one, 4,5-dichloro-4-cyclohexylisothiazolin-3-one, 2- (thiocyanomethylthio) benzothiazole, 2-mercaptobenzothiazole sodium, 2-mercaptobenzothiazole zinc, etc. Can do.
Examples of imidazole compounds include benzimidazole carbamate compounds, sulfur atom-containing benzimidazole compounds, and cyclic compound derivatives of benzimidazoles. Examples of the benzimidazole carbamate compound include methyl 1H-2-benzimidazole carbamate, methyl 1-butylcarbamoyl-2-benzimidazole carbamate, methyl 6-benzoyl-1H-2-benzimidazole carbamate, 6- (2 -Thiophenecarbonyl) -1H-2-benzimidazole carbamate methyl and the like. Examples of the sulfur atom-containing benzimidazole compound include 2,4-bis (4-thiazolyl) benzimidazole, 2- (4-thiazolyl) benzimidazole (TBZ) and the like.
The above antibacterial and antifungal inorganic compounds and organic compounds can be used alone or in combination of two or more.

As the antibacterial / antifungal agent (B), a composite of an inorganic compound and an organic compound in which one or more of the inorganic compound and the organic compound are supported between layered silicate layers is gradually released. In addition, imidazole antibacterial and antifungal agents and isothiazoline antibacterial and antifungal agents are preferred as organic compounds having antibacterial and antifungal properties, and are preferable because of their relatively low toxicity. Zinc ions are preferred from the same point as the mold-based inorganic compound.
The layered silicate is conventionally known, and can be used without particular limitation as long as it is a silicate having crystal layer units stacked on each other to form a layered structure, and is a natural product. May also be a composite. The particle size, water content, ion exchange capacity, color, etc. of the layered silicate are not particularly limited. For blending into the one-pack type moisture curable sealant composition that improves the antibacterial and antifungal properties of the outer wall joint top coating film of the present invention, a powder having an average particle size of 10 μm or less is preferable. A powder of 1 to 7 μm is more preferable, and a uniform particle size with a narrow particle size distribution is even more preferable.
A composite of an inorganic compound and an organic compound in which one or more of the inorganic compound and the organic compound, particularly the inorganic compound and the organic compound, are supported on the layered silicate (between). A commercially available product can be suitably used.

In addition, the antibacterial / antifungal agent (B) in the present invention has good storage stability of the one-component moisture-curable sealing material composition, and exhibits the antifungal property of the outer wall joint top coating film over a long period of time. Therefore, it is used by being dispersed in a high molecular weight dilution resin (C) described later . Ie, in advance, the inorganic compound or organic compound in the layered silicate (interlayer), an inorganic compound, especially by supporting one or more each of the inorganic compound and an organic compound and an organic The antibacterial / antifungal agent (B), which is a composite of an organic compound, is dispersed in the high molecular weight dilution resin (C) to form a fixed concentration antibacterial / antifungal agent (B) dispersion. An appropriate amount of the antibacterial / antifungal agent (B) dispersion is added to the isocyanate group-containing urethane prepolymer (A) for the preparation of the moisture curable sealant composition. The concentration of the antibacterial / antifungal agent (B) in the high molecular weight diluting resin (C) dispersion of the antibacterial / antifungal agent (B) can be arbitrarily set. From the viewpoint of operability, in the examples described later, 50% by mass is used. In order to prevent non-uniformity (for example, sedimentation, separation) in the high molecular weight dilution resin (C), such as when a low-mass% antibacterial and antifungal agent (B) dispersion is required, A wrinkle modification imparting agent such as colloidal silica, which will be described later, can also be used. The dispersion can be prepared by adding the antibacterial / antifungal agent (B) to the high molecular weight diluting resin (C) and dispersing the dispersion using a disperser such as a disper. Care must be taken to destroy the salt. The destruction of the layered silicate adversely affects the generation of bacteria and fungi on the outer wall joint top coat film over a long period of time.

  The compounding amount of the antibacterial / antifungal agent (B) is preferably 0.01 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer (A). When the blending amount of the antibacterial / antifungal agent (B) is less than 0.01 parts by mass, the antibacterial / antifungal effect tends to be insufficient, and blending exceeding 10 parts by mass is economically undesirable.

The resin for high molecular weight dilution (C) in the present invention dilutes the one-component moisture-curable sealant composition to reduce the viscosity and improve the workability, and also cures the one-component moisture-curable sealant composition. It is used to adjust the elastic properties of rubber, such as the modulus and elongation, and has excellent compatibility with the isocyanate group-containing urethane prepolymer (A). A resin that is liquid at room temperature with or without a polar group and having a number average molecular weight of 1,000 or more can be preferably mentioned. Examples of the polar group include an ester group, an ether group (oxyalkylene group), a urethane group, and the like and the number and the number of these groups may be included in the molecule alone or in combination. Also good. Further, the high molecular weight dilution resin (C) is preferably a compound that has substantially no active hydrogen group or isocyanate group having reactivity with an isocyanate group in the molecule.
Specifically, as the resin having a polar group, polyester resins from dicarboxylic acids and glycols, alkyl etherified derivatives and alkyl esterified derivatives of polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxypropylene glycol, Examples thereof include polyether-based resins of saccharide-based polyhydric alcohols, polyoxyalkylene-based resins such as liquid polyoxyalkylene-based urethane resins, and low-viscosity (meth) acrylic acid alkyl ester-based (co) polymer resins. Examples of the resin having no polar group include hydrocarbon resins such as polyolefin resins such as polybutadiene and polyisoprene, and polyalkylene resins such as hydrogenated polybutadiene and hydrogenated polyisoprene.
These can be used alone or in combination of two or more.
Among these, the saccharide-based polyvalent is low in terms of low viscosity, good compatibility with the isocyanate group-containing urethane prepolymer (A), and good workability of the resulting one-component moisture-curable sealing material composition. Polyether resins of alcohol, liquid polyoxyalkylene urethane resins, and low viscosity (meth) acrylic acid alkyl ester (co) polymer resins are preferred, and liquid polyoxyalkylene urethane resins and low viscosity (meth) are preferred. Acrylic acid alkyl ester (co) polymer resins are preferred, and liquid polyoxyalkylene urethane resins are particularly preferred.
The number average molecular weight of the high molecular weight dilution resin (C) is 1,000 to 200,000, more preferably 1,000 to 100,000, even more preferably 2,000 to 50,000, and particularly 2,000 to 20,000. Preferably, 2,000 to 10,000 are most preferable. If the number average molecular weight is less than 1,000, it tends to migrate (bleed) to the surface of the cured product, lowers the adhesion of the overcoated film, and further migrates to the surface of the coated film to adhere to the surface of the coated film. This is not preferable because it causes contamination due to adhesion. When the number average molecular weight exceeds 100,000, the viscosity of the high molecular weight diluting resin (C) is increased, and the workability of the resulting one-pack type moisture curable sealing material composition is deteriorated.

  Polysaccharides of saccharide polyhydric alcohols (polyoxyalkylene) resins include alkylenes such as ethylene oxide and propylene oxide for hydroxyl groups of saccharide polyhydric alcohols such as sucrose (sucrose), glucose, mannitol, sorbitol, etc. Examples include addition (co) polymerization of oxides, alkyl etherification or alkyl esterification, and end-capping with an alkyl group, and a resin having substantially no hydroxyl group in the molecule. SPX-80 manufactured by Sanyo Kasei Kogyo Co., Ltd. can be listed as a general commercial product of etherified resin.

The liquid polyoxyalkylene urethane resin is obtained by reacting a polyoxyalkylene alcohol and an organic isocyanate, contains a polyoxyalkylene group and a urethane group in the molecule, and has substantially no hydroxyl group or isocyanate group. High molecular weight resins are preferred. Furthermore, by making the molecular maximum distribution (Mw / Mn) of the liquid polyoxyalkylene urethane resin as narrow as 1.6 or less, particularly preferably 1.0 to 1.3, the wavy polyoxyalkylene urethane resin is increased. Even if it is molecular weight, a viscosity can be restrained low and workability | operativity of the one-pack type moisture curable sealing material composition obtained can be made favorable.
Specifically, polyoxyalkylene alcohol and organic isocyanate (preferably, polyoxyalkylene monool and organic polyisocyanate, or polyoxyalkylene polyol and organic monoisocyanate) are equivalent ratio of isocyanate group / hydroxyl group. In the range of 0.9 to 1.1 / 1.0, most preferably, it can be suitably produced by reacting at 1/1. When the equivalent ratio is less than 0.9 / 1.0, the hydroxyl group content increases, so that it reacts with the isocyanate group of the isocyanate group-containing urethane prepolymer (A) to increase the viscosity and deteriorate workability. If it exceeds 1 / 1.0, the content of isocyanate groups increases, which is not preferable in that the influence of the cured product on the rubber elastic properties cannot be ignored.

  The above-mentioned “substantially free of hydroxyl group or isocyanate group in the molecule” means that when synthesizing a polyether-based resin of saccharide-based polyhydric alcohol or a liquid polyoxyalkylene-based urethane resin, it depends on the molar ratio of raw materials. Although a small amount of hydroxyl group or isocyanate group may remain in the molecule, this means that there is no inconvenience even if it is assumed that no hydroxyl group or isocyanate group is contained in achieving the present invention.

Specific examples of the polyoxyalkylene alcohol include polyoxyalkylene monools, polyoxyalkylene polyols, and mixtures thereof.
Examples of the polyoxyalkylene monool include those obtained by ring-opening addition (co) polymerization of a cyclic ether compound to an initiator. The number average molecular weight of the polyoxyalkylene monool is preferably 500 to 50,000, more preferably 1,000 to 30,000, and particularly preferably 1,000 to 10,000. If the number average molecular weight is less than 500, the resulting liquid polyoxyalkylene urethane resin is likely to bleed. Therefore, if the number average molecular weight exceeds 50,000, the viscosity of the liquid polyoxyalkylene urethane resin increases, resulting in a one-part moisture. Since workability | operativity of a curable sealing material composition deteriorates, it is not preferable.
Specific examples of the initiator include low-molecular alkyl monoalcohols such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, tert-butanol, cyclohexanol, phenol, cresol and the like. Phenols, and mixtures of two or more of these. Of these, low molecular alkyl monoalcohols having 5 or less carbon atoms such as methanol and ethanol are preferred.
Examples of the cyclic ether compound include ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, and a mixture of two or more thereof. Of these, propylene oxide is preferred.
Further, the polyoxyalkylene monool is produced using the same catalyst as that used as the catalyst used for producing the polyoxyalkylene polyol used for the synthesis of the isocyanate group-containing urethane prepolymer (A). The total unsaturation is preferably 0.1 meq / g or less, more preferably 0.07 meq / g or less, particularly preferably 0.04 meq / g or less, and the molecular weight distribution [in terms of polystyrene by gel permeation chromatography (GPC) The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) = Mw / Mn] is 1.6 or less, particularly a narrow one of 1.0 to 1.3 is the liquid polyoxyalkylene urethane resin obtained. It is preferable in that the viscosity can be lowered and the workability of the resulting one-pack type moisture curable sealant composition is improved.
The “system” of the polyoxyalkylene monool is 50% by mass or more of the portion excluding the hydroxyl group in 1 mol of the molecule, more preferably 80% by mass or more, particularly preferably 90% by mass or more. Means that the remaining part may be modified with ester, urethane, polycarbonate, polyamide, poly (meth) acrylate, polyolefin, etc., but 95% by mass or more of the molecule excluding the hydroxyl group Is most preferably composed of polyoxyalkylene.
Examples of the polyoxyalkylene polyol include the same compounds as those used in the synthesis of the isocyanate group-containing urethane prepolymer (A).
These can be used alone or in combination of two or more.
Among these, the polyoxyalkylene monool is preferable in that the viscosity of the obtained liquid polyoxyalkylene urethane resin can be reduced, and the workability of the resulting one-pack type moisture curable sealant composition is improved. Polyoxypropylene monool is particularly preferable.

Specific examples of the organic isocyanate include organic monoisocyanates, organic polyisocyanates, and mixtures thereof, and further, compounds similar to those used for the synthesis of the isocyanate group-containing urethane prepolymer (A). It is done.
These can be used alone or in combination of two or more.
Of these, organic polyisocyanates are preferred in that the viscosity of the liquid polyoxyalkylene urethane resin obtained at a relatively low cost can be reduced, and the workability of the resulting one-pack moisture-curable sealing material composition is good. Furthermore, aliphatic polyisocyanate, alicyclic polyisocyanate and araliphatic polyisocyanate are preferable, araliphatic polyisocyanate is more preferable, xylylene diisocyanate is more preferable, and m-xylylene diisocyanate is most preferable.
In synthesizing the liquid polyoxyalkylene urethane resin, a compound similar to the curing acceleration catalyst described later can be used as a reaction catalyst. Furthermore, a well-known organic solvent can also be used.

Specifically, as the low-viscosity (meth) acrylic acid alkyl ester-based (co) polymer resin, a (meth) acrylic acid alkyl ester-based monomer and, if necessary, other ethylenically unsaturated compounds, Can be obtained by a known radical polymerization reaction such as batch polymerization or continuous polymerization at 50 to 350 ° C. in the presence or absence of a polymerization initiator and in the presence or absence of an organic solvent (co). A polymer resin, preferably a (co) polymer resin having a narrow molecular weight distribution and a low viscosity, which is obtained by a continuous high-temperature polymerization reaction at 100 to 300 ° C., has substantially no hydroxyl group or isocyanate group.
The (meth) acrylic acid alkyl ester-based (co) polymer resin has a polystyrene-reduced number average molecular weight of 1,000 to 50,000, more preferably 1,000 to 10,000, and particularly 1,000 by gel permeation chromatography. ˜5,000, Tg of 0 ° C. or less, further −100 to −20 ° C., viscosity at 25 ° C. of 50,000 mPa · s or less, further 100 to 10,000 mPa · s, especially 200 to 5,000 mPa · s Is preferred. If the number average molecular weight is less than 1,000, it tends to bleed on the surface of the cured product and deteriorates the adhesion of the top coat, which is not preferable, and the number average molecular weight is 50,000 and Tg is 0 ° C. When the viscosity exceeds 50,000 mPa · s, the workability of the one-component moisture-curable sealant composition is deteriorated, which is not preferable.
The (meth) acrylic acid alkyl ester (co) polymer resin may be obtained by polymerizing a (meth) acrylic acid alkyl ester monomer alone, or a (meth) acrylic acid alkyl ester monomer. Two or more kinds of the copolymer may be copolymerized, or a (meth) acrylic acid alkyl ester monomer and another ethylenically unsaturated compound may be copolymerized. Of these, (meth) acrylic acid alkyl ester copolymer resins are preferred because the resulting resin has a low viscosity.

Examples of (meth) acrylic acid alkyl ester monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate. 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic acid Cyclohexyl, cetyl (meth) acrylate, behenyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, ethoxylated phenol (meth) acrylate, ethoxylated paracumylphenol (meth) acrylate, ethoxylated nonylphenol (Meta) Acry Mono (meth) acrylic acid esters such as propoxylated nonylphenol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-phenoxy (meth) acrylate, etc. Monomer, ethoxylated bisphenol F di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, caprolactone di (meth) Acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, ethylene glyco Rudi (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Examples include poly (meth) acrylic acid ester monomers such as polypropylene glycol di (meth) acrylate, etc., and these can be used alone or in combination of two or more. Among these, a low molecular weight mono (meth) acrylic acid alkyl ester monomer having a molecular weight of less than 500 and further having a molecular weight of less than 300 is preferable in that a low viscosity high molecular weight dilution resin (C) is obtained. More preferred are methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
Examples of the ethylenically unsaturated monomer other than the (meth) acrylic acid ester monomer that can be used as necessary include, for example, ethylene, propylene, isobutylene, butadiene, chloroprene, vinyl chloride, vinylidene chloride, Examples include vinyl acetate, acrylonitrile, styrene, chlorostyrene, 2-methylstyrene, divinylbenzene, (meth) acrylamide, N-vinyl-pyrrolidone, and these can be used alone or in combination of two or more. Of these, styrene is preferred in the same manner as described above.

  The high molecular weight dilution resin (C) is preferably blended in an amount of 1 to 200 parts by weight, particularly 10 to 100 parts by weight, per 100 parts by weight of the isocyanate group-containing urethane prepolymer (A). If it is less than 1 part by mass, the effect of lowering viscosity with respect to the one-component moisture-curable sealing material composition is lost, and if it exceeds 200 parts by mass, durability of the cured product, such as heat resistance and water resistance, is not preferable.

The oxygen curable unsaturated compound (D) in the present invention is a compound having in its molecule an unsaturated group that reacts and cures with oxygen, such as in the air, and is blended in a one-pack type moisture curable sealing material composition. By this, since it transfers to the surface after hardening and forms a cured film and eliminates the adhesion of the hardened | cured material surface, the surface contamination prevention effect for a long term is exhibited. In addition, when a top coating is applied to the cured surface, the effect of remarkably improving the adhesion of the coating is also exhibited. This effect is also presumed to be because the oxygen-curable unsaturated compound (D) migrates to the surface of the cured product to form a thin cured film, and this film and the coating film of the overcoated paint adhere strongly.
Specific examples of the oxygen curable unsaturated compound (D) include drying oils, various modified products of drying oils, (co) polymer maleic acid modified products of diene compounds, and modified boil oils. In the molecule, such as a compound containing an oxygen curable unsaturated group and a polar group such as an ester group, or a (co) polymer of a diene compound has an oxygen curable unsaturated group but no polar group. Compound etc. are mentioned.

Examples of drying oils (including semi-drying oils in a broad sense) include paulownia oil, soybean oil, linseed oil, dehydrated castor oil, coconut oil, castor oil, and the like. And various alkyd resins obtained, (meth) acrylic (co) polymers modified with drying oil, epoxy resins, silicone resins, and the like.
Examples of (co) polymers of diene compounds include polymers of C _{4 to} C ₈ diene compounds such as 1,2-butadiene, 1,4-butadiene, 1,3-pentadiene, isoprene, chloroprene, and the like. Examples of the above-mentioned copolymers, or copolymers of these with other monomers such as styrene and acrylonitrile (SBR, NBR, etc.) and the like, as modified products of (co) polymers of diene compounds, Examples include maleic acid-modified products, boiled oil-modified products, and epoxy-modified products of (co) polymers of the diene compounds. Among these, (co) polymers that are liquid at room temperature are preferred.
These can be used alone or in combination of two or more.
Among these, when blended with a one-component moisture-curable sealant composition, the effect of improving the adhesion of the top coat is great, and in the molecule, oxygen-curable unsaturated groups and polar groups such as ester groups Are preferable, one or two or more selected from the group of drying oils and modified products of drying oils are preferable, drying oils are more preferable, and tung oil is most preferable.

  The oxygen curable unsaturated compound (D) can be used in combination with a catalyst for promoting an oxidative curing reaction or a metal dryer. Examples of these catalysts and metal dryers include salts of metals and organic acids such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate and zirconium octylate, and amine compounds.

  The oxygen curable unsaturated compound (D) is used in an amount of 0.01 to 50 parts by weight, further 0.1 to 20 parts by weight, particularly 1 to 20 parts by weight, based on 100 parts by weight of the isocyanate group-containing urethane prepolymer (A). It is preferable to do this. If it is less than 0.01 part by mass, the adhesion of the top coat is not sufficiently improved, and if it exceeds 50 parts by mass, the tensile properties of the cured product tend to be impaired.

  Additives in the present invention include fillers, high molecular weight plasticizers, weathering stabilizers, thixotropic agents, adhesion promoters, curing accelerators, storage stability improvers (dehydrating agents), colorants, solvents, and the like. Can be mentioned. Each of them can be used for reinforcement, weight increase, weather resistance, thixotropic property, adhesion improvement, curing rate adjustment, storage stability improvement, coloring, viscosity adjustment and the like.

Examples of fillers include mica, kaolin, zeolite, graphite, diatomaceous earth, white clay, clay, talc, slate powder, anhydrous silicic acid, quartz fine powder, aluminum powder, zinc powder, and synthetic silica such as precipitated silica, heavy Inorganic fillers such as calcium carbonate, light calcium carbonate, magnesium carbonate, alumina, calcium oxide, magnesium oxide, inorganic fillers such as asbestos, glass fibers, carbon fibers, etc., or their surface Fillers treated with organic substances such as fatty acids, wood flour, walnut flour, rice husk flour, pulp powder, cotton chips, rubber powder, polyamide resin, polyester resin, polyurethane resin, silicone resin, vinyl chloride resin, vinyl acetate resin , Polyolefin resin such as polyethylene and polypropylene, acrylic resin In addition to organic fillers such as thermoplastic resins such as epoxy resins, phenol resins, urea resins, melamine resins, or thermosetting resin powders, flame retardant fillers such as magnesium hydroxide and aluminum hydroxide, etc. Also mentioned. Moreover, the balloon which is a hollow substance is also mentioned, The shape is not only a spherical shape but also a cubic shape, a rectangular shape, a confetti shape, and a balloon that is slightly broken. Specifically, for example, inorganic balloons such as glass balloons, shirasu balloons, silica balloons, ceramic balloons, organic balloons such as phenol resin balloons, urea resin balloons, polystyrene balloons, polyethylene balloons, saran balloons, or inorganic compounds and organic balloons Examples thereof include a composite balloon in which a system compound is mixed or laminated. Also, those balloons coated or surface-treated can be used, for example, inorganic balloons surface-treated with a silane coupling agent described later, organic balloons calcium carbonate, talc, titanium oxide, etc. The thing coated with is also mentioned.
The blending amount of the filler is preferably 0 to 500 parts by mass, particularly 50 to 300 parts by mass with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer (A).

  Examples of the high molecular weight plasticizer include hydrocarbon polymers such as polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, and hydrogenated products thereof having a number average molecular weight of 500 or more.

The weathering stabilizer is used to prevent oxidation, photodegradation and thermal degradation after curing of the isocyanate group-containing urethane prepolymer (A), and to further improve not only the weather resistance but also the heat resistance. Specific examples of the weather resistance stabilizer include an antioxidant, an ultraviolet absorber, and a photocurable compound.
Specific examples of the antioxidant include hindered amine-based and hindered phenol-based antioxidants. Examples of the hindered amine-based antioxidant include bis (1,2,2,6,6-pentamethyl). -4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) Examples include sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine. In addition to Sanyo LS-292, trade names manufactured by Sankyo Co., Ltd., trade names Adeka Stub series LA-52, LA-57, LA-62, LA-67, LA-77, LA- 82, LA-87 and other low molecular weight hindered amine antioxidants with a molecular weight of less than 1,000, also LA-63P, LA-68LD or Ciba Specialty Chemicals' product names CHIMASSORB series 119FL, 2020FDL, 944FD, 944LD And high molecular weight hindered amine antioxidants having a molecular weight of 1,000 or more.
Examples of the hindered phenol antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-). tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], benzenepropanoic acid Examples include 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, and the like.
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers such as 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, and 2- (4,6-diphenyl- Triazine-based UV absorbers such as 1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, benzophenone-based UV absorbers such as octabenzone, 2,4-di-tert-butylphenyl Examples include benzoate-based ultraviolet absorbers such as -3,5-di-tert-butyl-4-hydroxybenzoate.
Examples of the photocurable compound include a compound containing one or more groups that are reactively cured by light such as an acryloyl group or a methacryloyl group in the molecule. ) Urethane (meth) acrylate reacted with acrylate compound, ester (meth) acrylate such as trimethylolpropane tri (meth) acrylate, polyester (meth) acrylate such as (meth) acrylate of polyethylene adipate polyol, ( Examples thereof include polyether (meth) acrylates such as (meth) acrylate, polyvinyl cinnamates, and azidated resins. Monomers and oligomers having a molecular weight of 10,000 or less, and a molecular weight of 5,000 or less are preferred. Meta) Acry Those are preferred which yl group average per molecule containing two or more.

The thixotropic agent imparts thixotropic properties to the one-component moisture-curing sealant composition that improves the antibacterial and antifungal properties of the outer wall joint coating on the outer wall of the present invention, and the composition is applied to the building outer wall, etc. It is used to prevent sagging (slump) when filled or coated on a vertical surface, for example, fine powder silica, inorganic thixotropic agent such as organic surface treated calcium carbonate, organic bentonite, Examples thereof include organic thixotropic agents such as modified polyester polyols and fatty acid amides. Among these, finely divided silica is preferable because it can impart thixotropy with a small amount of blending, but in order to increase the curing speed of the one-component moisture-curing sealant composition, thixotropic addition is provided. The structure may be destroyed, and care should be taken when using it because it causes sagging when filled or coated on a vertical surface. On the other hand, organic surface-treated calcium carbonate does not have such disadvantages and can impart stable thixotropy.
Examples of the finely divided silica include natural silica obtained by pulverizing quartz, silica sand, diatomaceous earth, and the like, and synthetic silica such as wet silica such as precipitated silica and dry silica such as fumed silica. Etc. Further, the properties of the silica particle surface include a hydrophilic property that is not treated with an organic substance and a hydrophobic property obtained by treating the particle surface with an organic silane compound such as dimethyldichlorosilane.
Examples of the organic surface-treated calcium carbonate include a finely powdered synthetic calcium carbonate called precipitated calcium carbonate and light calcium carbonate, or a heavy calcium carbonate surface obtained by pulverizing natural calcium carbonate into fine powder. For the purpose of imparting modification-modifying ability and preventing secondary aggregation, fatty acid, fatty acid alkyl ester, fatty acid metal salt, metal salt of resin acid such as rosin acid, reaction product of organic polyisocyanate and stearyl alcohol, described later And calcium carbonate treated with an organic compound such as a coupling agent similar to the silane coupling agent. Here, the fatty acid metal salt is preferably a sodium, potassium, calcium or aluminum salt of a fatty acid having 10 to 25 carbon atoms such as stearic acid. As these commercially available products, for example, white gloss flower CC, white gloss flower CCR, white gloss flower R06, VIGOT-10, VIGOT-15, STAVIGOT-15A (above manufactured by Shiroishi Kogyo Co., Ltd.), NCC # 3010, NCC # 1010 (above Nitto Flour Industry Co., Ltd.) Etc.). Of these, fatty acid surface-treated calcium carbonate is particularly preferred because of its high thixotropic effect.
The average particle diameter of the organic surface-treated calcium carbonate is preferably 0.01 to 0.5 μm, more preferably 0.03 to 0.15 μm, and the BET specific surface area is preferably 5 to 200 m ² / g, more preferably 10 to 60 m ² / g. When the average particle diameter is less than 0.01 μm or the BET specific surface area exceeds 200 m ² / g, the viscosity of the resulting one-component moisture-curing sealant composition is increased and workability is deteriorated. If it exceeds 0.5 μm or the BET specific surface area is less than 5 m ² / g, the thixotropic effect is lost, which is not preferable.

Examples of the adhesion imparting agent include various coupling agents such as silane, titanate, aluminum and zircoaluminate and / or partial hydrolysis condensates thereof, organic polyisocyanate, epoxy resin, phenol resin, alkyd resin, and the like. Can be mentioned.
Specific examples of the silane coupling agent include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane, ethyltrimethoxysilane, diethyldiethoxysilane, n-butyltrimethoxysilane, n -Hexyltriethoxysilane, n-octyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, hydrocarbon group-bonded alkoxysilanes such as cyclohexylmethyldimethoxysilane, dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, etc. Hydrocarbon group-bound isopropenoxysilanes, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyl Methylmethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-glycidoxy Propylmethyldiisopropenoxysilane, 3-glycidoxypropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltri Molecular weights of 500 or less, preferably 40, such as alkoxysilanes having functional groups such as methoxysilane, 3-acryloxypropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and isopropenoxysilanes The following low molecular weight compound and / or one or compounds of molecular weight 200 to 3,000 in two or more partial hydrolysis condensate of the silane coupling agent.

  Specific examples of the curing accelerating catalyst include organic metal compounds, amines, and the like. For example, divalent organic tin compounds such as tin octylate and tin naphthenate, dibutyltin dioctoate, dibutyltin dilaurate, and dibutyltin dichloride. Tetravalent organotin compounds such as acetate, dibutyltin dimaleate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin diversate, dibutyltin oxide, dibutyltin bis (triethoxysilicate), reaction product of dibutyltin oxide and phthalate , Dibutyltin bis (acetylacetonate), tin chelate EXCESTAR C-501 manufactured by Asahi Glass Co., zirconium tetrakis (acetylacetonate), titanium tetrakis (acetylacetonate), aluminum tris (acetylacetonate) ), Aluminum tris (ethyl acetoacetate), acetylacetone cobalt, acetylacetone iron, acetylacetone copper, acetylacetone magnesium, acetylacetone bismuth, acetylacetone nickel, acetylacetone zinc, acetylacetone manganese and other metal chelate compounds, and organic acid lead salts such as lead octylate , Titanates such as tetra-n-butyl titanate and tetrapropyl titanate, organic bismuth compounds such as bismuth octylate and bismuth versatate, primary amines such as butylamine and octylamine, dibutylamine and dioctylamine Secondary amines, monoethanolamine, diethanolamine, alkanolamines such as triethanolamine, diethylenetriamine, triethylene Primary amines such as tetramine, secondary amines, tertiary amines such as triethylamine, tributylamine, triethylenediamine, N-ethylmorpholine, or salts of these amines with carboxylic acid, kaolin clay, hydrochloric acid Inorganic phosphoric acid compounds such as ethyl phosphate, organic phosphoric acid acidic compounds such as 2-ethylhexyl acid phosphate, and salts thereof with amines. Among these, an organic tin compound and a metal chelate compound are preferable, a tin-based chelate compound is more preferable, and dibutyltin dilaurate is most preferable because the reaction rate is high and the liquid is relatively low in toxicity and volatility.

  Storage stability improvers (dehydrating agents) include low-molecular crosslinkable silyl group-containing compounds such as vinyltrimethoxysilane, calcium oxide, which react with moisture present in the one-component moisture-curable sealant composition, Examples thereof include p-toluenesulfonyl isocyanate.

  Examples of the colorant include inorganic pigments such as titanium oxide and iron oxide, organic pigments such as copper phthalocyanine, and carbon black.

  Examples of the solvent include conventionally known organic solvents such as aliphatic solvents such as n-hexane, alicyclic solvents such as cyclohexane, aromatic solvents such as toluene and xylene, and petroleum solvents that are mixtures thereof. Any of these can be used as long as they do not react with each component of the one-component moisture-curable sealant composition.

  The total amount of high molecular weight plasticizer, weathering stabilizer, thixotropic agent, adhesion promoter, curing accelerator, storage stability improver (dehydrating agent), colorant and solvent is the isocyanate group-containing urethane prepolymer. (A) 0 to 500 parts by mass, particularly 10 to 100 parts by mass is preferable with respect to 100 parts by mass.

  In the present invention, each additive component can be used alone or in admixture of two or more.

The content of the liquid component at room temperature with an average molecular weight of 500 or less in the one-component moisture-curable sealant composition is preferably 12% by mass or less.

The production method of the one-pack type moisture curable sealant composition for improving the antibacterial and antifungal properties of the outer wall joint top coat of the present invention is not particularly limited. Each component of the polymer, and optionally an oxygen curable unsaturated compound, and an additive, are charged in a stirring device that can block moisture such as stainless steel or iron, and mixed in a mixing device. Under normal pressure, under reduced pressure, under pressure, It can be produced by stirring and mixing batchwise or continuously under various conditions such as under a nitrogen stream. Examples of the stirring and mixing apparatus include a planetary mixer, a kneader, an agitator, a nauta mixer, and a line mixer.
The manufactured one-part moisture-curing sealant composition is thickened and cured by moisture. Therefore, in order to maintain the storage stability of the contents, it should be packed and sealed and stored. preferable. The container may be anything as long as it is capable of blocking moisture, and examples include various types of containers such as drum cans, metal or synthetic resin pail cans and bag-like containers, and paper or synthetic resin cartridge-like containers. It is done.

Next, the antibacterial and antifungal properties of the outer wall joint top coat are improved by using the one-part moisture curable sealant composition that improves the antibacterial and antifungal properties of the outer wall joint top coat of the present invention. Describes how to do this.
The one-part moisture-curing sealant composition that improves the antibacterial and antifungal properties of the outer wall joint top coat of the present invention is basically antibacterial no matter what the outer wall specifications are used for filling the joint. Although it can exhibit antifungal properties, it is preferably used in applications where the outer wall joint is overcoated. Chi words, filled with a one-part moisture curable sealant composition on the outer wall joints of the building structure, and then coating a paint on the outer wall surface of the building structure comprising outer wall joints and cured, the outer wall It is preferable to improve the antibacterial and antifungal properties of the joint coating on the joint. Specifically, in the outer wall specification composed of ALC board, ceramic siding (non-painted board), concrete, etc., where the top coat specification is common for waterproofness, weather resistance, durability and design, etc. It is effective and preferable, and is particularly preferable in the specification of the outer wall composed of an ALC plate. ALC (Autoclaved Light-weight aerated Concrete) refers to lightweight aerated concrete manufactured and controlled in an autoclave state, which means high temperature and high pressure and humidity curing. ALC board is a JIS A5416 “Lightweight Aerated Concrete” It is an industrialized product whose manufacturing and management methods are specified for “concrete panels”. The main raw materials for ALC plate are silica, cement, quicklime, and aluminum powder of foaming agent and water to make a mixed solution, which is poured into a mold (form) that incorporates a reinforced mat with a special rust prevention treatment as a reinforcing material. Foam by reaction. Cut into a predetermined size in a semi-cured state, cured by autoclaving and completely cured, and then subjected to side surface processing and surface processing to obtain a product. It is certified as a legally incombustible material because it uses inorganic materials as the main raw material. In addition, it has about one-quarter weight and light weight compared to concrete because it has air bubbles inside the panel, has excellent heat insulation performance, and prevents condensation. Contributes to improved performance and excellent sound insulation. The use of the ALC board having such properties is mainly used in houses and small-scale buildings, in which the main structure is an iron structure and ALC is used for the outer wall, and it is used as an outer wall, a roof, or a floor board. If it is specified as an outer wall, it must be painted for waterproofing. The outer wall surface is often multi-layered, such as undercoating (undercoating), intermediate coating (main material), and topcoating (upcoating). Inorganic coating, acrylic coating, acrylic urethane coating, acrylic silicone coating Water-based paints such as paint and fluorine paint can be listed.
Before filling the outer wall joint part of the building structure with the one-part moisture-curing sealant composition that improves the antibacterial and antifungal properties of the outer wall joint part top coat of the present invention, the outer wall joint part is compared with the outer wall joint part. The antibacterial and antibacterial properties of the outer wall joint top coating film of the present invention, which is applied to an ALC plate having a low surface strength to improve the surface strength and designed to prevent foaming when applied to an ALC plate having a porous surface. It is preferable to apply a primer such as an organic solvent solution of a moisture curable urethane resin dedicated to the one-pack type moisture curable sealant composition that improves moldability .

Synthesis Example 1 (Synthesis of isocyanate group-containing urethane prepolymer)
While flowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube and heating / cooling device, polyoxypropylene glycol (Asahi Glass Co., Ltd., Exenol 3021, number average molecular weight 3,200, molecular weight distribution (Mw / Mn ) 1.1-1.2) 340g, polyoxypropylene triol (Mitsui Chemicals, MN-4000, number average molecular weight 4,000, molecular weight distribution (Mw / Mn) 1.1-1.2) 100g , 90 g of petroleum solvent (Nippon Mining Co., Cactus Solvent) was charged, and 54 g of 4,4'-diphenylmethane diisocyanate (Nippon Polyurethane Industry, Millionate MT, molecular weight 250) was charged with stirring, and dibutyltin as a reaction catalyst. Add 0.05 g of dilaurate, react with stirring at 70-80 ° C. for 2 hours, and by titration Isocyanate group content is completed the reaction as it becomes less theoretical value (1.04 wt%), and cooled, to synthesize an isocyanate group-containing urethane prepolymer P.
The resulting isocyanate group-containing urethane prepolymer P was a viscous transparent liquid at room temperature with an isocyanate group content of 1.00% by mass and a viscosity of 32,000 mPa · s at 25 ° C.

Synthesis Example 2 (Synthesis of liquid polyoxypropylene urethane resin)
While flowing nitrogen gas through a reactor equipped with a stirrer, thermometer, nitrogen seal tube and heating / cooling device, polyoxypropylene monool (manufactured by Asahi Glass Co., Ltd., XS-M3000, number average molecular weight 3,243, molecular weight distribution (Mw / Mn) 1.0-1.1) 300 g (OH equivalent: 0.0925) was charged, and 0.1 g of dibutyltin dilaurate and m-xylylene diisocyanate (Takeda Pharmaceutical, Takenate 500, molecular weight 188) with stirring. After adding 9.1 g (NCO equivalent: 0.0968) (R value (NCO equivalent / OH equivalent = 1.05)), the mixture was heated and stirred at 70 to 80 ° C. for 4 hours. The reaction was terminated when the theoretical value (0.06% by mass) or less was reached, and a liquid polyoxypropylene urethane resin U was produced.
This liquid polyoxypropylene-based urethane resin U has a measured isocyanate group content of 0.04% by mass, a viscosity of 3,300 mPa · s / 25 ° C., a molecular weight distribution (Mw / Mn) of 1.0 to 1.1, normal temperature It was a clear liquid.

Example 1
100.0 g of the isocyanate group-containing urethane prepolymer P obtained in Synthesis Example 1 and antibacterial / antifungal agent a (made by Toagosei Co., Ltd., isothiazoline / imidazole series) while flowing nitrogen gas through a cooling device and a kneading vessel with a nitrogen seal tube / Layer silicate / zinc oxide antibacterial / antifungal powder; kabinone 940, layered silicate supported) and liquid polyoxypropylene urethane resin U obtained in Synthesis Example 2 at a mass ratio of 1: 1 by T. K. 0.8 g of a white turbid uniform dispersion (50 mass% dispersion) obtained by stirring at 2,000 rpm for 30 minutes with Robomix, 59.6 g of the liquid polyoxypropylene urethane resin U obtained in Synthesis Example 2, and petroleum Solvent (Nihon Mining Co., Cactus Solvent) 26.0 g, Titanium oxide 13.0 g, Tung Oil 4.0 g, 3-Glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM403) 1.0 g, hindered phenol System antioxidant (manufactured by Ciba Specialty Chemicals, IRGANOX 1010, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]) 4.0 g sequentially, 60 ° C. In the following, the contents were stirred and kneaded until uniform. Next, 137.0 g of fatty acid-treated calcium carbonate (Shiraishi Kogyo Co., Ltd., Hakujyo Hana CCR) dried in an oven at 80 to 100 ° C. for 1 day in advance and 0.02 g of dibutyltin dilaurate were sequentially added and further kneaded until uniform. . Next, the mixture was degassed under reduced pressure at 30 to 100 hPa, filled in a container, and sealed to prepare a paste-like one-component moisture-curable sealant composition.

Example 2
In the same manner as in Example 1, except that 2.4 g of the liquid polyoxypropylene-based urethane resin U dispersion of the antibacterial / antifungal agent a and 58.8 g of the liquid polyoxypropylene-based urethane resin U were used. Type moisture curable sealant composition was prepared.

Example 3
In the same manner as in Example 1, except that 3.8 g of the liquid polyoxypropylene urethane resin U dispersion of the antibacterial / antifungal agent a and 58.1 g of the liquid polyoxypropylene urethane resin U were used. Type moisture curable sealant composition was prepared.

Example 4
In the same manner as in Example 1, except that 7.6 g of the liquid polyoxypropylene urethane resin U dispersion liquid of the antibacterial / antifungal agent a and 56.2 g of the liquid polyoxypropylene urethane resin U were used. Type moisture curable sealant composition was prepared.

Comparative Example 1
In Example 3, the liquid polyoxypropylene urethane resin obtained in Synthesis Example 2 and the antibacterial / antifungal agent a 1.9 g without using the liquid polyoxypropylene urethane resin U dispersion of the antibacterial / antifungal agent a A paste-like one-component moisture-curable sealant composition was prepared in the same manner except that 60.0 g of U was added separately.

Comparative Example 2
In Example 1, a paste-like one-component moisture-curable sealant composition was prepared in the same manner except that the antibacterial / antifungal agent a was not used.

Comparative Example 3
In Comparative Example 2, instead of liquid polyoxypropylene urethane resin U60.0 g, liquid polyoxypropylene urethane resin U30.0 g and diisononyl phthalate (Shin Nihon Rika Co., Ltd., DINP, molecular weight 419) 30.0 g were used. In the same manner as above, a paste-like one-component moisture-curable sealant composition was prepared.

Comparative Example 4
In Example 2, instead of the liquid polyoxypropylene urethane resin U dispersion of the antibacterial / antifungal agent a, the antibacterial / antifungal agent b (manufactured by Genri Kaken Co., Ltd., zirconium phosphate-silver / thiazole / haloalkylthio type) / Imidazole / Urea antibacterial / antifungal agent powder; except for using 2.4 g of liquid polyoxypropylene urethane resin U dispersion (50% by mass dispersion) of Hello Coat GK, layered silicate not supported) Thus, a paste-like one-component moisture-curable sealant composition was prepared.

Performance test (1) Extrudability JIS A1439: (1997, revised 2002) Evaluation was made by “4.14 Extrusion test with cartridge for test” in “Testing method of sealing material for building”.
The case where the extrusion time was 5 seconds or less was evaluated as ◯, and the case where it exceeded 5 seconds was evaluated as x.
(2) Slump JIS A1439: (1997, revised 2002) Slump (longitudinal) at 23 ° C. and 50% RH was measured according to “4.1 Slump Test” in “Testing Method of Sealant for Building”.
(3) Tack-free time JIS A1439: (1997, revised 2002) Measures tack-free time at 23 ° C and 50% RH in accordance with "4.19 Tack-free test" in "Testing methods for sealing materials for construction". did.
(4) Storage stability The viscosity ratio by a cone plate E type rotational viscometer (30 times cone, 10 rpm, 25 ° C.) was evaluated. The viscosity before heat treatment and the viscosity after standing for 5 days in a 50 ° C. constant temperature bath are measured, and (Viscosity value after 5 days at 50 ° C.) / (Viscosity value before heat treatment) is 1.3 or less. A value exceeding 3 and less than 1.5 was evaluated as Δ, and 1.5 or more was evaluated as ×.
(5) Antibacterial and antifungal properties A test specimen was prepared as follows.
Unpainted (specifications);
A 5 mm thick slate plate was used to produce a joint having a width of 25 mm, a depth of 15 mm, and a length of 150 mm. The joint was filled with the one-component moisture-curable sealant composition, and the excess composition was scraped off with a spatula to finish the surface flat. Next, it was cured for 14 days in a standard state (23 ° C. and 50% relative humidity), and the one-pack type moisture curable sealant composition was cured to obtain a test specimen. The surface on which the joint of the test body was formed was directed to the north, and the length direction of the test body was installed perpendicular to the ground surface (north surface 90 ° outdoor exposure). Separately, this specimen was directed south, and the specimen was installed with the length direction of the specimen inclined 30 ° with respect to the ground surface (exposure to the south 30 ° outdoors).
Painting (specification);
A 5 mm thick slate plate was used to produce a joint having a width of 25 mm, a depth of 15 mm, and a length of 150 mm. The joint was filled with the one-component moisture-curable sealant composition, and the excess composition was scraped off with a spatula to finish the surface flat. Next, it is cured for 14 days in a standard state (23 ° C. and 50% relative humidity), and the sealing material composition is cured, and a water-based acrylic silicone paint (manufactured by Fujikura Kasei Co., Ltd., ceramic tone flex, coating amount: top coat and intermediate coat) 300 to 500 g / m ² ) was applied with a brush, and further cured for 14 days in a standard state (23 ° C., 50% relative humidity) to obtain a test specimen. The surface on which the joint of the test body was formed was directed to the north, and the length direction of the test body was installed perpendicular to the ground surface (north surface 90 ° outdoor exposure). Separately, this specimen was directed south, and the specimen was installed with the length direction of the specimen inclined 30 ° with respect to the ground surface (exposure to the south 30 ° outdoors).
About the evaluation, the test body which exposed the said test body to the outdoor exposure stand installed in the site of Auto Chemical Industry Co., Ltd. for two years between May 2007 and May 2009 was evaluated. In the case of unpainted (specification), visually observe the cured surface of the one-component moisture-curing sealant composition, black and gray spots due to bacteria and mold, no contamination, ○, partly due to bacteria and mold Black-gray stains, Δ when contamination is observed, and black-gray stains due to bacteria and fungi, and x when contamination is observed. In the case of painting (specification), visually observe the surface of the joint coating film on the joint, and if there is no black-gray stain or contamination due to bacteria or mold, ○, partly black-gray stain due to bacteria or mold, contamination When it was seen, Δ was marked with a black and gray stain due to bacteria, mold, and contamination.
(6) Contamination Preparation of test specimen:
A 5 mm thick slate plate was used to produce a joint having a width of 25 mm, a depth of 15 mm, and a length of 150 mm. The joint was filled with the one-component moisture-curable sealant composition, and the excess composition was scraped off with a spatula to finish the surface flat. Next, it is cured for 14 days in a standard state (23 ° C. and 50% relative humidity) to cure the one-pack type moisture curable sealant composition, and a water-based acrylic silicone paint (manufactured by Fujikura Kasei Co., Ltd., Ceramic Tone Flex, coating) Amount: 300-500 g / m ² of each of the top coat and the intermediate coat was applied with a brush, and further cured for 14 days in a standard state (23 ° C., 50% relative humidity) to obtain a test specimen.
Next, after heat-treating a test body for 30 days in an 80 degreeC thermostat, it took out from the thermostat and sprinkled black silica sand (particle diameter of 70-110 micrometers) on the surface of the test body. Immediately, the specimen was turned over and the surface was lightly struck by hand to remove excess black silica sand. The state of black silica sand (dirt) remaining on the surface was visually observed to evaluate the contamination.
Judgment criteria;
○: The surface of the water-based acrylic silicone paint on the surface is clean with no black silica sand attached.
X: A state in which black silica sand adheres to the surface of the water-based acrylic silicone paint surface on the surface and becomes dirty.
(7) Paint adhesion Using a flexile plate having a size of about 150 mm × 100 mm and a thickness of 5 mm, a one-component moisture-curing sealant composition was applied to the surface with a thickness of about 3 mm, What was hardened and cured for 14 days at 50% relative humidity was produced. Next, the surface of the cured one-component moisture-curable sealant composition is brushed with a water-based acrylic silicone paint (manufactured by Fujikura Kasei Co., Ltd., ceramic tone flack, coating amount: 300 to 500 g / m ² for each of top coat and intermediate coat). The specimen was cured by curing for 14 days at 23 ° C. and 50% relative humidity.
Next, according to JIS K 5600-5-6 (1999) “General test method of paint, Part 5: Mechanical properties of coating film, Section 6: Adhesiveness (cross-cut method)”, the interval between cutting edges The test was conducted using a 2 mm multi-blade cutting tool, and the adhesion of the coating film was evaluated according to the following criteria.
Evaluation criteria (numerical value is the number of grids to which the coating is attached);
○: 20-25 / 25
X: 19 or less / 25
(8) Tensile adhesiveness JIS A1439: (1997, revised 2002) One-part moisture-curing sealing using a test specimen specified in “4.21 Tensile adhesiveness test” of “Testing method for architectural sealant” The material composition was placed, and after curing at 50 ° C. and 80% relative humidity for 3 days, the material composition was allowed to stand at 23 ° C. and 50% relative humidity for 1 day, and then measured under the same conditions. The adherend was slate, the primer was OP-15A (isocyanate group-containing urethane resin-containing one-part primer, manufactured by Auto Chemical Industries), and the open time was 20 minutes.

Claims (11)

Antibacterial properties of the outer wall joint top coating film, comprising an isocyanate group-containing urethane prepolymer (A) and a dispersion in which an antibacterial / antifungal agent (B) is dispersed in a high molecular weight dilution resin (C) ; A one-component moisture-curing sealant composition that improves mold resistance ,
The antibacterial and antifungal properties of the above outer wall joint top coating film, wherein the antibacterial and antifungal agent (B) is a composite in which a layered silicate is loaded with an antibacterial and antifungal compound . -Pack type moisture curable sealant composition for improving the quality. The antibacterial properties of the outer wall joint top coating film according to claim 1, wherein the content of the component liquid at normal temperature having an average molecular weight of 500 or less in the one-component moisture-curable sealant composition is 12% by mass or less. A one-component moisture-curable sealant composition that improves mold resistance. The antibacterial and antifungal properties of the outer wall joint top coating film according to claim 1 or 2, wherein the high molecular weight dilution resin (C) is a liquid resin at room temperature having a number average molecular weight of 1,000 or more. A one-component moisture-curing sealant composition for use. The one-pack type moisture curable sealant composition for improving the antibacterial and antifungal properties of the outer wall joint top coating film according to claim 3, wherein the resin is a urethane resin. The one-component moisture-curing property that improves the antibacterial and antifungal properties of the outer wall joint top coating film according to claim 4, wherein the urethane resin is a reaction product of a polyoxyalkylene alcohol and an organic isocyanate. Sealant composition. Furthermore, the one-part type moisture curable which improves the antibacterial property and antifungal property of the outer wall joint part top coat film as described in any one of Claims 1-5 containing an oxygen curable unsaturated compound (D). Sealant composition. The antibacterial and antibacterial properties of the outer wall joint top coating film according to claim 6, wherein the oxygen curable unsaturated compound (D) is one or more selected from the group consisting of a drying oil and a modified product thereof. A one-component moisture-curable sealant composition that improves moldability. Furthermore, the one-pack type moisture curable sealing material composition which improves the antibacterial property and antifungal property of the outer wall joint part top coat film as described in any one of Claims 1-7 containing an additive. The additive is selected from the group consisting of a filler, a high molecular weight plasticizer, a weathering stabilizer, a wrinkle modifier, an adhesion promoter, a curing accelerator, a storage stability improver, a colorant and a solvent, The one-pack type moisture curable sealant composition for improving the antibacterial and antifungal properties of the outer wall joint top coating film according to claim 8, wherein the composition is two or more. Filling the outer wall joint part of the building structure with a one-component moisture-curing sealant composition that improves the antibacterial and antifungal properties of the outer wall joint part topcoat film according to any one of claims 1 to 9. Then, a method of improving the antibacterial and antifungal properties of the outer wall joint top coating film, characterized in that a paint is applied to the outer wall surface of the building structure including the outer wall joint and cured. Before filling the outer wall joint of the building structure with a one-component moisture-curable sealant composition that improves the antibacterial and antifungal properties of the outer wall joint top coat, apply a primer to the outer wall joint. The method of improving the antibacterial property and antifungal property of the outer wall joint part top coat of Claim 10 which do.